EP0478909B1 - Verfahren zur Herstellung einer Diamantschicht und Anlage hierfür - Google Patents

Verfahren zur Herstellung einer Diamantschicht und Anlage hierfür Download PDF

Info

Publication number
EP0478909B1
EP0478909B1 EP91112188A EP91112188A EP0478909B1 EP 0478909 B1 EP0478909 B1 EP 0478909B1 EP 91112188 A EP91112188 A EP 91112188A EP 91112188 A EP91112188 A EP 91112188A EP 0478909 B1 EP0478909 B1 EP 0478909B1
Authority
EP
European Patent Office
Prior art keywords
arrangement
process according
cathode
anode
inlet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91112188A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0478909A1 (de
Inventor
Johann Dr. Karner
Erich Dr. Bergmann
Helmut Daxinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
OC Oerlikon Balzers AG
Original Assignee
Balzers AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Balzers AG filed Critical Balzers AG
Publication of EP0478909A1 publication Critical patent/EP0478909A1/de
Application granted granted Critical
Publication of EP0478909B1 publication Critical patent/EP0478909B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C23C16/45565—Shower nozzles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/272—Diamond only using DC, AC or RF discharges
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/277—Diamond only using other elements in the gas phase besides carbon and hydrogen; using other elements besides carbon, hydrogen and oxygen in case of use of combustion torches; using other elements besides carbon, hydrogen and inert gas in case of use of plasma jets
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C23C16/45572—Cooled nozzles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C23C16/45578—Elongated nozzles, tubes with holes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/503—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using DC or AC discharges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32055—Arc discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32321—Discharge generated by other radiation
    • H01J37/3233—Discharge generated by other radiation using charged particles

Definitions

  • the present invention relates to a method for producing a diamond layer on a good by means of a reactive, plasma-assisted coating process, a vacuum treatment system for the production of diamond layers with a vacuum recipient, an inlet arrangement opening therein for a working gas which is at least partially reacted in the recipient and a suction arrangement for gaseous reaction products and a method for setting the temperature on a holding element for a diamond-to-be-coated material in a plasma coating chamber.
  • the arc discharge takes place at low voltages, due to the small anode / cathode spacing at approx. 20V and at high currents in the order of 40A.
  • the arrangement of the goods is, however, arranged far outside of the plasma generated by this arc with a high power density.
  • the plasma density generated in this way is therefore not used at all for the coating process.
  • the process is carried out at about 3500 Pa process atmospheric pressure.
  • the process pressure is between 700 and 28000 Pa.
  • said method is characterized in accordance with the characterizing part of claim 1.
  • a system according to the invention for this is distinguished by the wording of claim 29.
  • working gas with the gas component to be reacted is injected linearly into the treatment recipient.
  • a carrier for the material to be coated is arranged outside the anode / cathode section.
  • the vacuum diamond coating system on which the present invention is based is based on the insight that this known type of arc discharge generation is outstandingly suitable for solving the above-mentioned task when the material to be coated is introduced into the anode / cathode path, that is to say in the area of the greatest plasma density.
  • the coating arrangement known from CH-A-664 768 is suitable for diamond coating.
  • FIG. 1 schematically shows a first embodiment variant of a treatment chamber for diamond coating.
  • a vacuum treatment container 1 the material 5 to be coated is placed on a holder 3 in the form of one or, as shown, several workpieces.
  • the holder 3 defines a storage area for the material to be coated, here a storage level E G.
  • the holder 3, and therefore opposite the surface E G is provided on the recipient 1 with an inlet arrangement 7 for the working gas or gas mixture R with reaction gas or gas mixture.
  • the inlet arrangement 7 comprises an area-wide arrangement of inlet openings 9 in a plate 11, which are fed from a pressure compensation chamber 13, which, facing the plate 11 away from the reaction space V of the recipient 1, is itself gas-fed through one or more supply lines 15.
  • the holder 3 is designed like a table and is supported on the recipient wall by means of insulation 17. Below the holder 3, a suction line 19 is provided for evacuating the recipient 1 and, during the treatment process, for suctioning off gaseous reaction products or used working gas.
  • a DC voltage necessary to maintain an arc discharge B is applied, by means of a DC voltage generator 29.
  • the heating of the hot cathode 25 takes place, with electrical heating, by means of a generator 31.
  • This generator can be a Act a direct or alternating current generator, possibly with a downstream isolating transformer.
  • the volume of the pressure equalization chamber 13 is so large that there is a uniform pressure distribution of the gas supplied through the line 15 with respect to the inlet openings 9, and by distributing the inlet openings, their flow cross sections and their axial length, and consequently their flow resistances and their mouth direction specifically effects a desired, essentially directed inflow distribution of the gas into the recipient 1.
  • an essentially uniform gas outflow directed against the holder 3 is achieved by uniform distribution and formation of the openings 9 on the plate 11.
  • the working gas admitted into the reaction space V partially reacts therein to an increasing degree over time, and used working gas is drawn off through line 19.
  • reaction areas V along dash-dot areas E2 each give essentially the same ratio of unused working gas to used working gas. Due to the fact that the holder 3 positions the material to be coated on such a surface, a uniform coating effect distribution is achieved at least on surface areas of the material that are equidistant from this surface.
  • the recipient 1 is preferably formed on all sides from a material which does not impair the coating process, preferably from quartz glass.
  • the holder 3 and consequently the material are preferably not placed at a specific electrical potential, but, as illustrated with the insulating supports 17, are operated in a floating manner, so that an electrical potential can be established in accordance with the potential distribution in the reaction space V. As a result becomes the coating temperature of the good lowered compared to the case in which the good would be kept at anode potential.
  • the arc discharge produced in the manner shown is a long low-voltage discharge which, at pressures of only a few Pa, has a low DC voltage, e.g. below 150V, usually at voltages of the order of magnitude of the ionization energy of the working gas mixture.
  • the cathode chamber 23 is preferably, e.g. through a line 33, a purge gas.
  • the pressure in the cathode chamber 23 can be set such that it is slightly higher than the working pressure in the reaction space V, which results in a gas outflow from the chamber 23.
  • a neutral plasma current exits the ionization chamber into the coating chamber, i.e. an equal number of ions as electrons.
  • a process-compatible gas is introduced as the purge gas, usually noble gases, Ar or He.
  • Fig. 1a the bracket 3 of Fig. 1 is shown in detail.
  • the holder 3 is preferably connected to a reference potential, for example anode potential, by a current branch 35, via a resistance element 37.
  • a reference potential for example anode potential
  • the potential of the material, decoupled from the arc current can be adjusted by an adjustable voltage source 39 between anode and cathode potential in space V.
  • an adjustable voltage source 39 between anode and cathode potential in space V.
  • the material temperature is also adjusted by adjusting the material potential, decoupled from the discharge.
  • the temperature of the holder 3 is tapped, as is immediately clear to the person skilled in the art, an electrical signal corresponding to it is compared with a desired value, and the resistance value of the resistance element 37 and / or voltage value at the voltage source 39 are each set as regulating elements.
  • the product temperature can be tracked according to a predefined time characteristic.
  • the suction 19 does not have to be carried out centrally, but can also take place peripherally and / or distributed.
  • FIG. Another system is shown schematically in FIG.
  • the gas inlet is not designed to be distributed, but the arc discharge.
  • a hot cathode chamber arrangement 23a is provided on the coating container 1, here cubically, to which the working gas R is supplied via a terminally perforated supply line 41, in this case not distributed over an area, which extends along a cuboid wall of the container 1.
  • One or more hot cathodes 25 are provided therein, with a surface distribution.
  • the cathode chamber arrangement 23a which can of course also be separate, appropriately distributed chambers, is connected to the reaction space V of the recipient 1 via a plurality of diaphragm openings 21a.
  • the rectangular or square-shaped anode 27a is arranged in the recipient, opposite the screens 21a.
  • a support grid 3 for goods to be coated 5 is provided transversely to the direction of discharge, the suction device 19 on the cuboid side facing the working gas supply 41.
  • the several arc discharges here distributed over a wide area, result in areas along E B for some coating requirements Sufficiently uniform coating, despite the fact that the working gas supply is not evenly distributed.
  • the uniformity of the coating can be influenced by targeted distribution of the discharges. With E3 areas are entered, along which the plasma density is substantially constant, with equally distributed and operated anode / cathode sections.
  • the spatial plasma distribution in the reaction space V is influenced by targeted flat or spatial distribution and / or control of individual or grouped anodes / cathode sections.
  • the spatial diamond layer distribution can be adjusted either by deliberately distributing the working gas inlet over a large area or by deliberately distributing the arc discharges spatially, so that large-area goods or many can be treated simultaneously, even three-dimensionally.
  • both the gas inlet is carried out with a targeted areal distribution and the arc discharges are generated in a spatially distributed manner.
  • a preferred system is described below.
  • FIG. 3 This procedure is shown in principle in FIG. 3, in which an arc discharge B between a hot cathode arrangement 23b and an anode arrangement 27b takes place in a substantial volume area of a reaction space V b of a recipient 1b in the same direction C as the consumption direction V R defined between the working gas inlet and suction of the reaction gas.
  • Such preferred exemplary embodiments are then shown which, combined, show the procedures according to FIGS. 1, 2 and 3.
  • the recipient 1 has a cylinder wall 2 made of quartz.
  • the reaction space V delimited by the wall 2 is closed on the one hand by the inlet arrangement 7 with openings 9 for fresh working gas R.
  • an anode plate 27c with an electrically insulating wall part 8 forms the pressure distribution chamber 13
  • the fresh working gas R being connected through a line connection 15a with center opening 16 is inserted through the anode plate 27c into the pressure distribution chamber 13.
  • a plurality of good carriers or substrate carrier grids 3a are arranged on planes which are essentially perpendicular to the recipient axis A.
  • the reaction space V is closed off by an orifice plate 24 with outlet orifices 21c for the schematically entered arc discharges B.
  • the hot cathode chamber 23c is provided adjoining the diaphragm plate 24, in which, for example, on the periphery, a hot cathode coil 25c directly heated with heating current I H rotates.
  • a low-voltage generator is connected between anode plate 27c and hot cathode 25c.
  • flushing gas lines 33c open, whereby a flushing gas, such as argon or helium, is let into the hot cathode area.
  • the gas which is let into the area of the hot cathode 25c protects the cathode from the effects of the coating process. This results in a much longer service life for the hot cathode.
  • the hot cathode 25c is surrounded by a coaxial diaphragm 40 with radially directed openings 42. This enables a pressure gradation towards the center.
  • the end of the cathode chamber 23c is closed by a cover part 44, with a central suction line 19c.
  • the aperture plate 24 is cooled (not shown).
  • the screen 40 is preferably made of tantalum or a ceramic.
  • the inlet openings 9 preferably uniformly distributed, the working gas R admitted into the reaction space V.
  • the arc discharge is maintained from the diaphragm openings 21c, which are, for example, equally distributed and, via the openings 9 of the arrangement 7, the anode 27c.
  • gaseous reaction products flow through the aperture openings 21c, in countercurrent to the electron current of the arc discharge, and through the central region of the cathode chamber 23c from the suction line 29c.
  • the workpieces are e.g. substrate carrier grids 3a operated in a floating manner or, for temperature control or regulation via a current branch, as explained with reference to FIG. 1a, connected to a reference potential or a control voltage source.
  • FIG. 5 shows a currently preferred embodiment variant of a coating chamber used according to the invention in greater detail.
  • the reference symbols previously used are used for parts or units already described.
  • the actual recipient 1 with quartz glass wall 2 is closed on one side by the inlet arrangement 7.
  • a relatively large-diameter perforated, cooled anode plate 50 is arranged, spaced apart and insulated from the plate 11.
  • a further perforated plate 52 for better gas distribution arranged.
  • the electrical supply 54 for the anode is provided centrally.
  • the pressure distribution chamber is formed here by two pressure levels between the two distribution plates 52 and 11.
  • the anode plate 50 is designed to be as little disruptive as possible for the working gas, so as to be “transparent” so that on the one hand it does not disrupt its flow and on the other hand as little as possible is affected or coated by this gas.
  • This arrangement achieves an optimally homogeneous gas distribution at the gas inlets 9 of the same design and at the same time ensures cooling of the anode 50.
  • Heating rods 58 can optionally be provided outside the recipient 1.
  • magnetic coils 60 are provided outside the recipient and coaxially to the anode / cathode path in order to optimize the plasma distribution in the reaction space V with the product carriers 3a by means of magnetic DC or AC fields.
  • the actual recipient with provided heaters 58 is closed by an outer wall 62.
  • FIG. 6 schematically shows a further coating chamber used for the method according to the invention, in which the extraction of both flushing gas and let in by the schematically illustrated one Inlet 68, as well as the working gas, is let in as described, through the inlet 15, peripherally.
  • the reference symbols already used are used, with which the arrangement shown here can be readily understood by the person skilled in the art.
  • a higher pressure is set in the ionization chamber or cathode chamber than in the treatment room. A particularly effective ionization of the gas is thereby achieved. Because the gas in the ionization chamber 23 is essentially a noble gas, the life of the cathode is drastically increased.
  • the suction takes place at the suction connections 72.
  • FIG. 7 shows, schematically, the electrically operated system parts of the arrangement according to the invention. These include one or, as shown, a plurality of hot cathodes 25, one or more anodes 27, one or more crop carriers 3 for the crop to be treated.
  • the coating systems shown for reactive, low-voltage arc plasma-assisted diamond coating work with low anode / cathode voltages, for example below 150 V, with high discharge currents per well carrier area, for example over 4000 A / m2, and result in low treatment temperatures, essentially below 900 ° C. There are high plasma densities at low treatment temperatures.
  • Silicon substrates pretreated with diamond paste with the dimensions 20 x 10 x 1 mm were placed on a substrate grid with a diameter of 360 mm, which was located between the cathode and the anode.
  • the substrate grid was electrically isolated together with the substrates of the cathode and anode.
  • the coating recipient was evacuated to a pressure of ⁇ 0.1 Pa. After the plasma was ignited in a pure argon atmosphere, with 20% of the argon being let in through the ionization chamber or hot cathode chamber and 80% through the anode (the Ar flow was 90% of the total flow), 9% H2 was added through the anode .
  • the hot cathodes Since part of the argon flow was admitted through the ionization chamber and because there was a higher pressure than in the coating room due to the orifices in the lid of the hot cathode chamber, the hot cathodes were flushed with argon and were not directly exposed to the H2 flow. As a result, the hot cathodes have a long service life. So they could be used for twenty 10-hour coating runs.
  • the substrates were located directly in the plasma between the anode and cathode.
  • the arc current was set to approx. 650 A - which corresponds to a current per substrate support area of approx. 6.4 kA / m2 - so that the substrates were heated to a temperature of 800 ° C in plasma.
  • the arc voltage was 70 V
  • the floating potential of the substrates was 35 V below the anode potential.
  • 1% CH4 was added to the process gases.
  • Mass flow controllers were used to measure the gas flows of the various gases.
  • the coating pressure was set to 400 Pa by regulating the pumping speed of the vacuum pump.
  • the coating temperature which was measured with thermocouples, was kept at 800 ° C. by fine control of the arc current (FIG. 1a). After a coating time of 5 hours, the substrates were cooled and removed from the recipient.
  • the layers thus produced showed sharp-edged crystals with a grain size of 0.5 to 5 »m that had grown together in a scanning electron microscope to form a dense layer, the crystals primarily exhibiting a [100] faceting.
  • the layer thickness was 5 »m.
  • the diamond peak at 1333 cm-1 was detected in the Raman spectrum.
  • the lattice plane spacings determined from the electron diffraction image of a layer detached from the substrate corresponded to the lattice plane spacings of the diamond structure.
  • the CH4 flow is relatively high compared to other diamond coating processes because part of the gas was consumed at the large-area anode by the anode-side gas inlet. Because of the low coating temperature, an amorphous carbon layer is deposited on it due to its intensive cooling.
  • Pretreated silicon substrates were placed on the substrate grid, which was connected to the anode via an ohmic resistor. After heating in an Ar / H2 atmosphere, 1% CH4 was again added. An arc current of approx. 600 A was set, corresponding to a current density per substrate carrier area of approx. 5.9 kA / m2, and a current I of approx. 0.5 A per cm2 of coating area via the resistor (FIG. 1a) Subtrate stripped and the substrate support grid.
  • the process time was 5 hours at a coating temperature of 800 ° C.
  • the layers again showed crystals with [100] faceting.
  • the possibility of precise temperature control with the substrate carrier flow made a more precise process control possible.
  • the coating process was carried out as in Example 2, but the potential of the substrates, instead of the variable resistance, was set by an additional DC voltage generator between the cathode and the substrate grid.
  • the advantage of this arrangement is that the plasma power is decoupled from the coating temperature: With constant parameters of the arc that determines the excitation of the gas particles, the coating temperature can be set independently of this.
  • silicon substrates measuring 15 x 20 x 1 mm were placed on an upper substrate support grid, and carbide indexable inserts were placed on an underlying substrate support grid with the usual dimensions of 12.7 x 12.7 x 2 mm. Since small substrates in the plasma are heated up more than large surfaces, a different current I (FIG. 1a) was required to set the same temperature on the two substrate levels, which current could be set by the separate voltage supply for the individual substrate grids. Diamond layers with [100] faceting could be deposited both on the silicon substrates and on the indexable inserts.
  • Silicon substrates were used as substrates without pretreatment with abrasives. When the process was carried out as in Example 1, diamond layers could be deposited again, but the seed density was lower than in the case of pretreated substrates. There were fewer, but larger crystals.
  • the coating process was carried out with a gas composition of 60% Ar, 33% H2 and 7% CH4 at a coating temperature of 800 ° C.
  • the arc voltage was 100 V.
  • the process pressure was 400 Pa, the silicon substrates were at floating potential.
  • the arc voltage increased with the higher H2 content in the plasma, but the arc became unstable with the increased addition of CH4, so that the arc had to be re-ignited several times.
  • Ceramic indexable inserts were coated at a pressure of 20 Pa and a temperature of 780 ° C.
  • the gas composition was 9% H2, 2% CH4 and 89% Ar.
  • the arc current was 620 A with an arc voltage of 70 V.
  • 11 »m thick layers could be deposited.
  • the layer consisted of the "ball-like" diamond crystals known from the literature, which are formed at higher CH4 flows.
  • the coating process was carried out as in Example 2, but CO2 was used as additional coating gas (Ar 88%, H2 9%, CH4 1%, CO2 2%).
  • the diamond content in the layers could be increased, as can be seen from the Raman spectra.
  • the layers produced in this way had a pronounced [111] faceting.
  • the coating process was carried out as in Example 7, but O2 was used as an additional coating gas instead of CO2.
  • the gas composition was 89% Ar, 9% H2, 1.5% CH4 and 0.5% O2.
  • the layers had a pronounced [111] faceting.
  • Example 2 The coating process was carried out as in Example 1, but the gases H2 and CH4 were not admitted through the anode, but rather directly into the coating space through a gas supply at floating potential. In this configuration, too, diamond layers could be deposited on silicon substrates. Less CH4 flow was required because the anode did not have as much gas consumption as the CH4 anodic inlet.
  • Example 2 The same arrangement as in Example 1 was chosen and the same parameters were set. However, the arc current was regulated to 750 A, with an arc voltage of 80 V, so that the coating temperature was 900 ° C. The layers deposited in this way no longer showed sharp-edged crystals, but a soft, graphite-like black layer.
  • Example 3 The process was carried out as in Example 3, but the coating temperature at the start of the coating process was kept lower than during the coating process. As a result, a better quality of the crystals near the substrate was achieved, which was demonstrated by SEM images.
  • This example shows that the optimal coating temperature in the seed formation phase is different than in the subsequent growth process. At the same coating temperature in the seed formation phase as in the crystal growth phase Structure of the crystals near the substrates not as sharp as at a distance from the substrate surface.
  • the plasma was not evenly distributed across the substrate grid.
  • the plasma density in the radial direction of the arc was greatly reduced towards the outside.
  • diamond layers could also be deposited, however, due to the different plasma density, the parameters that were necessary for the deposition in the diamond structure were strongly dependent on the radial position of the substrates. Therefore, diamond layers could be deposited in a small area, but a homogeneous coating over larger areas was not possible.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Chemical Vapour Deposition (AREA)
  • Mounting, Exchange, And Manufacturing Of Dies (AREA)
  • Physical Vapour Deposition (AREA)
  • Carbon And Carbon Compounds (AREA)
EP91112188A 1990-09-14 1991-07-20 Verfahren zur Herstellung einer Diamantschicht und Anlage hierfür Expired - Lifetime EP0478909B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4029270 1990-09-14
DE4029270A DE4029270C1 (enrdf_load_stackoverflow) 1990-09-14 1990-09-14

Publications (2)

Publication Number Publication Date
EP0478909A1 EP0478909A1 (de) 1992-04-08
EP0478909B1 true EP0478909B1 (de) 1995-01-25

Family

ID=6414298

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91112188A Expired - Lifetime EP0478909B1 (de) 1990-09-14 1991-07-20 Verfahren zur Herstellung einer Diamantschicht und Anlage hierfür

Country Status (6)

Country Link
US (1) US5616373A (enrdf_load_stackoverflow)
EP (1) EP0478909B1 (enrdf_load_stackoverflow)
JP (1) JP3348865B2 (enrdf_load_stackoverflow)
AT (1) ATE117738T1 (enrdf_load_stackoverflow)
DE (2) DE4029270C1 (enrdf_load_stackoverflow)
ES (1) ES2067099T3 (enrdf_load_stackoverflow)

Families Citing this family (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4339326A1 (de) * 1993-11-19 1995-05-24 Winter Cvd Technik Gmbh Abrichtrolle für Schleifscheiben
US5587207A (en) 1994-11-14 1996-12-24 Gorokhovsky; Vladimir I. Arc assisted CVD coating and sintering method
US5478608A (en) * 1994-11-14 1995-12-26 Gorokhovsky; Vladimir I. Arc assisted CVD coating method and apparatus
US5753045A (en) * 1995-01-25 1998-05-19 Balzers Aktiengesellschaft Vacuum treatment system for homogeneous workpiece processing
DE59603312D1 (de) * 1995-01-25 1999-11-18 Balzers Ag Liechtenstein Verfahren zur reaktiven Schichtabscheidung
CH692446A5 (de) 1996-04-15 2002-06-28 Esec Sa Verfahren zur Herstellung von Werkstücken und von Teilen hierfür
RU2111292C1 (ru) * 1997-07-02 1998-05-20 Борис Николаевич Пыпкин Способ получения алмазоподобных покрытий
EP1033746A4 (en) * 1997-11-20 2003-05-28 Tokyo Electron Ltd PLASMA DEPOSITION OF A FILM
SE9804538D0 (sv) * 1998-12-23 1998-12-23 Jensen Elektronik Ab Gas discharge tube
KR100302457B1 (ko) 1999-04-06 2001-10-29 박호군 다이아몬드 막 증착방법
CH694699A5 (de) * 1999-04-29 2005-06-15 Balzers Hochvakuum Verfahren zur Herstellung von Silizium.
JP4806146B2 (ja) * 1999-07-13 2011-11-02 エリコン・トレーディング・アクチェンゲゼルシャフト，トリュープバッハ 真空処理ないしは粉末製造のための装置および方法
US6410101B1 (en) 2000-02-16 2002-06-25 Motorola, Inc. Method for scrubbing and passivating a surface of a field emission display
DE10018143C5 (de) * 2000-04-12 2012-09-06 Oerlikon Trading Ag, Trübbach DLC-Schichtsystem sowie Verfahren und Vorrichtung zur Herstellung eines derartigen Schichtsystems
US6502530B1 (en) * 2000-04-26 2003-01-07 Unaxis Balzers Aktiengesellschaft Design of gas injection for the electrode in a capacitively coupled RF plasma reactor
DE20013526U1 (de) * 2000-08-05 2000-12-07 Avdel Verbindungselemente GmbH, 30851 Langenhagen Vorrichtung zum Verbinden von Blechen durch Stanznieten oder Durchsetzfügen
DE10149588B4 (de) 2001-10-08 2017-09-07 Oerlikon Trading Ag, Trübbach Verfahren zur Diamantbeschichtung von Substraten
EP1361437A1 (en) * 2002-05-07 2003-11-12 Centre National De La Recherche Scientifique (Cnrs) A novel biological cancer marker and methods for determining the cancerous or non-cancerous phenotype of cells
US7560657B2 (en) * 2002-05-08 2009-07-14 Btu International Inc. Plasma-assisted processing in a manufacturing line
US7494904B2 (en) * 2002-05-08 2009-02-24 Btu International, Inc. Plasma-assisted doping
US7465362B2 (en) * 2002-05-08 2008-12-16 Btu International, Inc. Plasma-assisted nitrogen surface-treatment
US7497922B2 (en) * 2002-05-08 2009-03-03 Btu International, Inc. Plasma-assisted gas production
US20050233091A1 (en) * 2002-05-08 2005-10-20 Devendra Kumar Plasma-assisted coating
US7638727B2 (en) * 2002-05-08 2009-12-29 Btu International Inc. Plasma-assisted heat treatment
WO2003095237A1 (en) * 2002-05-08 2003-11-20 Leonhard Kurz Gmbh & Co. Kg Method of decorating large plastic 3d objects
US7445817B2 (en) * 2002-05-08 2008-11-04 Btu International Inc. Plasma-assisted formation of carbon structures
US20060062930A1 (en) * 2002-05-08 2006-03-23 Devendra Kumar Plasma-assisted carburizing
US20060233682A1 (en) * 2002-05-08 2006-10-19 Cherian Kuruvilla A Plasma-assisted engine exhaust treatment
US20060057016A1 (en) * 2002-05-08 2006-03-16 Devendra Kumar Plasma-assisted sintering
US7432470B2 (en) 2002-05-08 2008-10-07 Btu International, Inc. Surface cleaning and sterilization
US7498066B2 (en) * 2002-05-08 2009-03-03 Btu International Inc. Plasma-assisted enhanced coating
US20060228497A1 (en) * 2002-05-08 2006-10-12 Satyendra Kumar Plasma-assisted coating
US20060237398A1 (en) * 2002-05-08 2006-10-26 Dougherty Mike L Sr Plasma-assisted processing in a manufacturing line
BR0309814A (pt) * 2002-05-08 2005-03-01 Dana Corp Métodos de formação de plasma
US7189940B2 (en) 2002-12-04 2007-03-13 Btu International Inc. Plasma-assisted melting
US7866342B2 (en) 2002-12-18 2011-01-11 Vapor Technologies, Inc. Valve component for faucet
US8220489B2 (en) 2002-12-18 2012-07-17 Vapor Technologies Inc. Faucet with wear-resistant valve component
US7866343B2 (en) * 2002-12-18 2011-01-11 Masco Corporation Of Indiana Faucet
US6904935B2 (en) 2002-12-18 2005-06-14 Masco Corporation Of Indiana Valve component with multiple surface layers
US8555921B2 (en) 2002-12-18 2013-10-15 Vapor Technologies Inc. Faucet component with coating
JP4280603B2 (ja) * 2003-11-04 2009-06-17 キヤノン株式会社 処理方法
ES2380699T3 (es) * 2004-06-08 2012-05-17 Dichroic Cell S.R.L. Sistema para la deposición química en fase de vapor asistida por plasma de baja energía
US20080129208A1 (en) * 2004-11-05 2008-06-05 Satyendra Kumar Atmospheric Processing Using Microwave-Generated Plasmas
US20060105106A1 (en) * 2004-11-16 2006-05-18 Applied Materials, Inc. Tensile and compressive stressed materials for semiconductors
US20070026205A1 (en) 2005-08-01 2007-02-01 Vapor Technologies Inc. Article having patterned decorative coating
DE102010000388A1 (de) * 2010-02-11 2011-08-11 Aixtron Ag, 52134 Gaseinlassorgan mit Prallplattenanordnung
GB201021870D0 (en) * 2010-12-23 2011-02-02 Element Six Ltd A microwave plasma reactor for manufacturing synthetic diamond material
US10304665B2 (en) 2011-09-07 2019-05-28 Nano-Product Engineering, LLC Reactors for plasma-assisted processes and associated methods
US9761424B1 (en) 2011-09-07 2017-09-12 Nano-Product Engineering, LLC Filtered cathodic arc method, apparatus and applications thereof
DE102012024340A1 (de) * 2012-12-13 2014-06-18 Oerlikon Trading Ag, Trübbach Plasmaquelle
US10247661B2 (en) * 2016-07-20 2019-04-02 Cook Medical Technologies Llc Optical technique for coating characterization
US11834204B1 (en) 2018-04-05 2023-12-05 Nano-Product Engineering, LLC Sources for plasma assisted electric propulsion
US20220127721A1 (en) * 2020-10-23 2022-04-28 Applied Materials, Inc. Depositing Low Roughness Diamond Films

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2538987A1 (fr) * 1983-01-05 1984-07-06 Commissariat Energie Atomique Enceinte pour le traitement et notamment la gravure de substrats par la methode du plasma reactif
US4509451A (en) * 1983-03-29 1985-04-09 Colromm, Inc. Electron beam induced chemical vapor deposition
JPS60118693A (ja) * 1983-11-25 1985-06-26 Mitsubishi Metal Corp ダイヤモンドの低圧合成方法
US4731255A (en) * 1984-09-26 1988-03-15 Applied Materials Japan, Inc. Gas-phase growth process and an apparatus for the same
CH664768A5 (de) * 1985-06-20 1988-03-31 Balzers Hochvakuum Verfahren zur beschichtung von substraten in einer vakuumkammer.
DE3614398A1 (de) * 1985-07-01 1987-01-08 Balzers Hochvakuum Anordnung zum behandeln von werkstuecken mit einer evakuierbaren kammer
US4859490A (en) * 1986-07-23 1989-08-22 Sumitomo Electric Industries, Ltd. Method for synthesizing diamond
US4851254A (en) * 1987-01-13 1989-07-25 Nippon Soken, Inc. Method and device for forming diamond film
JPH02167891A (ja) * 1988-12-20 1990-06-28 Citizen Watch Co Ltd ダイヤモンド膜気相合成装置
US5094878A (en) * 1989-06-21 1992-03-10 Nippon Soken, Inc. Process for forming diamond film

Also Published As

Publication number Publication date
JP3348865B2 (ja) 2002-11-20
DE4029270C1 (enrdf_load_stackoverflow) 1992-04-09
ATE117738T1 (de) 1995-02-15
EP0478909A1 (de) 1992-04-08
DE59104388D1 (de) 1995-03-09
JPH04231397A (ja) 1992-08-20
US5616373A (en) 1997-04-01
ES2067099T3 (es) 1995-03-16

Similar Documents

Publication Publication Date Title
EP0478909B1 (de) Verfahren zur Herstellung einer Diamantschicht und Anlage hierfür
DE4029268C2 (de) Verfahren zur gleichspannungs-bogenentladungs-unterstützten, reaktiven Behandlung von Gut und Vakuumbehandlungsanlage zur Durchführung
DE3881077T2 (de) Verfahren zur herstellung eines diamantfilms.
DE69815348T2 (de) Vorrichtung und verfahren zur keimbildung und abscheidung von diamant mittels heissdraht-dc-plasma
DE3875815T2 (de) Methode zur behandlung der substratoberflaechen mit hilfe von plasma und reaktor fuer die durchfuehrung dieser methode.
DE69605280T2 (de) Verfahren zum aufbringen diamantähnlicher kohlenstoff-filme
DE69617134T2 (de) Vorrichtungen zum Aufdampfen oder Ätzen
EP2148939B1 (de) Vakuumbehandlungsanlage und vakuumbehandlungsverfahren
DE3884653T2 (de) Verfahren und Vorrichtung zur Gasphasenabscheidung von Diamant.
DE19505268C2 (de) CVD-Verfahren zur Beschichtung von Substratoberflächen
EP0988407B1 (de) Verfahren zur herstellung von werkstücken, die mit einer epitaktischen schicht beschichtet sind
WO1986007391A1 (en) An apparatus for coating substrates by plasma discharge
DE3614384A1 (de) Verfahren zur beschichtung von substraten in einer vakuumkammer
DE2823876A1 (de) Verfahren zum verdampfen von material in einer vakuumaufdampfanlage
EP0275018A2 (de) Verfahren und Vorrichtung zum Beschichten elektrisch leitender Gegenstände mittels Glimmentladung
DE10018143A1 (de) DLC-Schichtsystem sowie Verfahren und Vorrichtung zur Herstellung eines derartigen Schichtsystems
DE4025396A1 (de) Einrichtung fuer die herstellung eines plasmas
DE29615190U1 (de) Anlage zur Beschichtung von Werkstücken
WO1999014390A2 (de) Verfahren zur sputterbeschichtung von oberflächen
DE3941202A1 (de) Verfahren zur erzeugung von schichten aus harten kohlenstoffmodifikationen und vorrichtung zur durchfuehrung des verfahrens
DE69619075T2 (de) Plasmatempern von Dünnschichten
EP0734459B1 (de) Verfahren und einrichtung zum plasmaaktivierten bedampfen
DE69110547T2 (de) Plasma-CVD-Anlage.
DE102013107659B4 (de) Plasmachemische Beschichtungsvorrichtung
DE69516673T2 (de) Verfahren und gerät zur beschichtung eines substrats

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19920320

17Q First examination report despatched

Effective date: 19931013

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT CH DE ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 117738

Country of ref document: AT

Date of ref document: 19950215

Kind code of ref document: T

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950203

REF Corresponds to:

Ref document number: 59104388

Country of ref document: DE

Date of ref document: 19950309

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2067099

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
ITF It: translation for a ep patent filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20030707

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20030711

Year of fee payment: 13

Ref country code: AT

Payment date: 20030711

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20030716

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20030730

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20030731

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20030813

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20030918

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040720

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040720

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040721

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050201

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050201

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20040720

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050331

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20050201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050720

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20040721